Degree Of Fluorination Research Articles

Synthesis of tungsten oxo fluoroalkoxide complexes WO(OR)3L as precursors for growth of WOx nanomaterials by aerosol-assisted chemical vapor deposition

Partially fluorinated oxo-alkoxide tungsten complexes bearing β-diketonate or ketoesterate ligands have been synthesized and their thermal and physical properties have been evaluated for Aerosol Assisted Chemical Vapor Deposition (AACVD) of WOx. Volatility and thermal stability of the complexes have been shown to depend on the bidentate ligand and the degree of fluorination of the alkoxides. Growth of tungsten oxide from the precursor WO(OC(CH3)2CF3)3(tbac) (tbac=tert-butyl acetoacetate) has been demonstrated. Deposits grown at temperatures from 150 to 300°C are amorphous thin films of substoichiometric WOx. Deposition at temperatures from 350 to 500°C produced either polycrystalline films or crystalline nanorods of W18O49.

Side-chain fluorination on the pyrido[3,4-b]pyrazine unit towards efficient photovoltaic polymers

A series of new polymer donors (PT-PP, PT-2 f PP and PT-4 f PP) were synthesized based on alkylthiophene substituted benzodithiophene (BDT-T) and pyrido[3,4- b ]pyrazine (PP) building blocks and the effects of fluorination on the polymer properties were explored. Photophysical properties, charge mobilities and morphologies of the three polymers have been intensively investigated. The results indicated that the introduction of the fluorine atom at meta - positions of phenyl substituted PP unit hardly affected their highest occupied molecular orbital (HOMO) level. More importantly, controlling the degree of side-chain fluorination in the polymers is crucial for optimizing the blend morphology. Three polymers showed different photovoltaic properties. The polymer solar cell (PSC) based on the single layer device structure of ITO/PEDOT:PSS/PT-4 f PP:PC71BM (1:1, w : w )/ZrAcac/Al demonstrates a high power conversion efficiency (PCE) of 7.61% under the illumination of AM 1.5G, 100 mW cm−2, which is the highest value for PP-based PSCs.

Synthesis of Polyflourinated Biphenyls; Pushing the Boundaries of Suzuki-Miyaura Cross Coupling with Electron-Poor Substrates.

Polyfluorinated biphenyls are interesting and promising substrates for many different applications. Unfortunately, all current methods for the syntheses of these compounds only work for a hand full of molecules or only in very special cases. Thus, many of these compounds are still inaccessible to date. Here we report a general strategy for the synthesis of a wide range of highly fluorinated biphenyls. In our studies we investigated crucial parameters, such as different phosphine ligands and the influence of various nucleophiles and electrophiles with different degrees of fluorination. These results extend the scope of the already very versatile Suzuki–Miyaura reaction toward the synthesis of very electron-poor products, making these more readily accessible. The presented methodology is scalable and versatile without the need for elaborate phosphine ligands or Pd-precatalysts.

The Influence of Backbone Fluorination on the Dielectric Constant of Conjugated Polythiophenes

AbstractThe ability to modify or enhance the dielectric constant of semiconducting polymers can prove valuable for a range of optoelectronic and microelectronic applications. In the case of organic photovoltaics, increasing the dielectric constant of the active layer has often been suggested as a method to control charge generation, recombination dynamics, and ultimately, the power conversion efficiencies. In this contribution, the impact that the degree and pattern of fluorination has on the dielectric constant of poly(3‐octylthiophene) (P3OT), a more soluble analogue of the widely studied conjugated material poly(3‐hexylthiophene), is explored. P3OT and its backbone‐fluorinated analogue, F‐P3OT, are compared along with a block and alternating copolymer version of these materials. It is found that the dielectric constant of the polymer thin films increases as the degree of backbone fluorination increases, in a trend consistent with density functional theory calculations of the dipole moment.

Click Chemistry Derived Pyridazines: Electron-Deficient Building Blocks with Defined Conformation and Packing Structure.

A series of 3,6-bis(4-triazolyl)pyridazines equipped with terminal phenyl substituents with varying degree of fluorination were synthesized by using the facile copper-catalyzed azide-alkyne cycloaddition and their structures were thoroughly investigated in the gas phase, in solution, and in the solid state by employing DFT calculations, NMR spectroscopy, and single-crystal X-ray diffraction, respectively. On the molecular level, their structure is governed by the strong preference of the triazole-pyridazine linkages for the anti-conformation. The supramolecular organization of the molecules in the crystalline solid is controlled by π-stacking, C-H⋅⋅⋅π as well as C-F⋅⋅⋅H interactions. The latter can conveniently be tuned by the number and position of fluorine substituents in the terminal phenyl units, giving rise to either herringbone-like, 1D or 2D lamellar packing. Electrochemistry and optical spectroscopy of all compounds suggest that they might find use as electron-transporting/hole-blocking materials in organic electronics.

Effect of the Hydrofluoroether Cosolvent Structure in Acetonitrile-Based Solvate Electrolytes on the Li+ Solvation Structure and Li-S Battery Performance.

We evaluate hydrofluoroether (HFE) cosolvents with varying degrees of fluorination in the acetonitrile-based solvate electrolyte to determine the effect of the HFE structure on the electrochemical performance of the Li-S battery. Solvates or sparingly solvating electrolytes are an interesting electrolyte choice for the Li-S battery due to their low polysulfide solubility. The solvate electrolyte with a stoichiometric ratio of LiTFSI salt in acetonitrile, (MeCN)2-LiTFSI, exhibits limited polysulfide solubility due to the high concentration of LiTFSI. We demonstrate that the addition of highly fluorinated HFEs to the solvate yields better capacity retention compared to that of less fluorinated HFE cosolvents. Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that HFEs exhibiting a higher degree of fluorination coordinate to Li+ at the expense of MeCN coordination, resulting in higher free MeCN content in solution. However, the polysulfide solubility remains low, and no crossover of polysulfides from the S cathode to the Li anode is observed.

Synthesis and Crystal Structures of Volatile Neptunium(IV) β-Diketonates.

Production of certified reference materials in support of domestic nuclear forensics programs require volatile precursors for introduction into electromagnetic isotopic separation instruments. β-Diketone chelates of tetravalent actinides are known for their high volatility, but previously developed synthetic approaches require starting material (NpCl4) that is prohibitively difficult and hazardous to prepare. An alternative strategy was developed here that uses controlled potential electrolysis to reduce neptunium to the tetravalent state in submolar concentrations of hydrochloric acid. Four different β-diketone ligands of varying degrees of fluorination were reacted with an aqueous solution of Np4+. Products of this reaction were characterized via X-ray diffraction and infrared spectroscopy, and were found to be neutral 8-coordinate complexes that adopt square antiprismatic crystal geometry. Synthesis of Np β-diketonates by this approach circumvents the necessity of using NpCl4 in tetravalent Np coordination compound synthesis. The volatility of the complexes was assessed using thermogravimetric analysis, where the temperature of sublimation was determined to be in the range of 180° to 205 °C. The extent of fluorination did not appreciably alter the sublimation temperature of the complex. Thermal decomposition of these compounds was not observed during sublimation. High volatility and thermal stability of Np β-diketonates make them ideal candidates for gaseous introduction into isotopic separation instruments.

Accomplishment of Multifunctional π-Conjugated Polymers by Regulating the Degree of Side-Chain Fluorination for Efficient Dopant-Free Ambient-Stable Perovskite Solar Cells and Organic Solar Cells.

We present an efficient approach to develop a series of multifunctional π-conjugated polymers (P1-P3) by controlling the degree of fluorination (0F, 2F, and 4F) on the side chain linked to the benzodithiophene unit of the π-conjugated polymer. The most promising changes were noticed in optical, electrochemical, and morphological properties upon varying the degree of fluorine atoms on the side chain. The properly aligned energy levels with respect to the perovskite and PCBM prompted us to use them in perovskite solar cells (PSCs) as hole-transporting materials (HTMs) and in bulk heterojunction organic solar cells (BHJ OSCs) as photoactive donors. Interestingly, P2 (2F) and P3 (4F) showed an enhanced power conversion efficiency (PCE) of 14.94%, 10.35% compared to P1 (0F) (9.80%) in dopant-free PSCs. Similarly, P2 (2F) and P3 (4F) also showed improved PCE of 7.93% and 7.43%, respectively, compared to P1 (0F) (PCE of 4.35%) in BHJ OSCs. The high photvoltaic performance of the P2 and P3 based photovotaic devices over P1 are well correlated with their energy level alignment, charge transporting, morphological and packing properties, and hole transfer yields. In addition, the P1-P3 based dopant-free PSCs and BHJ OSCs showed an excellent ambient stability up to 30 days without a significant drop in their initial performance.

Fluorination of Donor-Acceptor Copolymer Active Layers Enhances Charge Mobilities in Thin-Film Transistors.

Several recent reports have demonstrated that fluorinated analogues of donor/acceptor copolymers surpass nonfluorinated counterparts in terms of performance in electronic devices. Using a copolymer series consisting of fluorinated, partially fluorinated, and nonfluorinated benzotriazole, we confirm that the addition of fluorine substituents beneficially impacts charge transport in polymer semiconductors. Transistor measurements demonstrated a factor of 5 increase in carrier mobilities with the degree of fluorination of the backbone. Furthermore, grazing-incidence X-ray diffraction data indicates progressively closer packing between the conjugated cores and an overall greater amount of π-stacking in the fluorinated materials. It is likely that attractive interactions between the electron-rich donor and fluorinated electron-deficient acceptor units induce very tightly stacking crystallites, which reduce the energetic barrier for charge hopping. In addition, a change in crystallite orientation was observed from primarily edge-on without fluorine substituents to mostly face-on with fluorinated benzotriazole.

Mechanism of resistive switching in films based on partially fluorinated graphene

The mechanism of resistive switching in films of partially fluorinated graphene is investigated. The films are obtained on the basis of a number of graphene suspensions with different composition and various degree of fluorination. The dependence of the value of resistive switching on the presence of organic additives (N-methylpyrrolidone and dimethylformamide) in the suspension composition and the degree of fluorination are found experimentally. It is shown that, for films obtained from a suspension without organic components, no resistive switching is observed independently of the degree of fluorination. The most profound effect of ~10–20 times is found for films containing dimethylformamide. A physical model for the films is proposed; according to this model, the dependence under observation is related to the presence of encapsulated functional groups formed from dimethylformamide molecules manifesting electrical activity in the investigated films. The measured current–voltage characteristics of the films are described in the best way by the Frenkel–Poole model with an activation energy of 0.08 eV of centers responsible for conduction. The value of switching depends on the degree of fluorination of the initial suspensions. The greatest effect is observed at a degree of fluorination of the suspensions of ~CF 0.25. Suspensions of partially fluorinated graphene investigated in this study are suitable for fabricating device structures by the 2D-printing technology.

Lanthanide Fluorobenzoates as Bio-Probes: a Quest for the Optimal Ligand Fluorination Degree.

The thorough study of fluorinated benzoates of lanthanides (Eu, Tb, Nd, Er, Yb, Gd, La, Lu) is reported. Their composition in single crystal and powder state revealed two predominant structural motifs. An in-depth luminescence study has been performed on the reported fluorobenzoates, showing, that terbium and europium complexes in solid state possess high luminescence intensity with the quantum yield of up to 69 %. High solubility in most organic solvents, as well as in water, combined with the high luminescence intensity in water solution and non-toxicity allowed the testing of europium complexes as bioprobes in cellulo. Among all tested fluorobenzoates, europium 2-fluorobenzoate dihydrate combined the best luminescent properties, thermodynamic stability, aqueous solubility, and non-toxicity, and was shown to be a viable bio-marker.

Tuning the Catalytic Alkyne Metathesis Activity of Molybdenum and Tungsten 2,4,6-Trimethylbenzylidyne Complexes with Fluoroalkoxide Ligands OC(CF3)nMe3–n (n = 0–3)

The molybdenum and tungsten 2,4,6-trimethylbenzylidyne complexes [MesC≡M{OC(CF3)nMe3–n}3] (M = Mo: MoF0, n = 0; MoF3, n = 1; MoF6, n = 2; MoF9, n = 3; M = W: WF3, n = 1; Mes = 2,4,6-trimethylphenyl) were prepared by the reaction of the tribromides [MesC≡MBr3(dme)] (dme = 1,2-dimethoxyethane) with the corresponding potassium alkoxides KOC(CF3)nMe3–n. The molecular structures of all complexes were established by X-ray diffraction analysis. The catalytic activity of the resulting alkylidyne complexes in the homometathesis and ring-closing alkyne metathesis of internal and terminal alkynes was studied, revealing a strong dependency on the fluorine content of the alkoxide ligand. The different catalytic performances were rationalized by DFT calculations involving the metathesis model reaction of 2-butyne. Because the calculations predict the stabilization of metallacyclobutadiene (MCBD) intermediates by increasing the degree of fluorination, MoF9 was treated with 3-hexyne to afford the MCBD complex [(C3Et3)Mo{...

Negative differential resistance in partially fluorinated graphene films

Partially fluorinated graphene films were created by chemical functionalization of graphene layers in an aqueous solution of hydrofluoric acid. The formation of graphene islands or graphene quantum dots (GQDs) and a fluorinated graphene network is demonstrated in such films. Negative differential resistance (NDR) resulting from the formation of the potential barrier system in the films was observed for different fluorination degrees of suspension. The origin of the NDR varies with an increase in the fluorination degree of the suspension. Numerical calculations were performed to elucidate the tunneling between adjacent energy levels and creation of NDR. It was found that in the case of films with smaller flake and smaller GQD sizes, multi-peak NDR appears in the I–V curve. We predict that the NDR peak position shifts towards lower voltage with a decrease in the GQD size. Surprisingly, we observed a negative step-like valley for positive biases in the I-V curve of samples. Our findings with detailed analysis shed light on understanding the mechanisms of the NDR phenomenon in a partially fluorinated graphene system.

The preparation of surface fluorinated polyethylene films with excellent properties similar to that of fluoropolymers

Various surface fluorinated polyethylene films with different fluorination degree have been prepared by direct fluorination. The chemical structure of the resulted fluorinated polyethylene layer has been effectively tuned by direct fluorination, where the fluorination degree and chemical structures are highly dependent on fluorination temperature. Direct fluorination with low temperature mainly results in a formation of CHF groups, whereas CF2 groups are prevailing at high temperature, which plays a major role in the enhancement of weathering-resistant properties. The polyethylene films with highly fluorinated layers show better weathering-resistant property, which are much more stable against UV irradiation compared with the virgin. Moreover, better thermal stability could also been observed in air atmosphere (up to 428.8°C) compared with the virgin (396.6°C) for the fluorinated layer. The increasing fluorination degree also results in lower surface energy (from 34.5 to 14.3mNm−1, 58.6% reduction), and higher contact angle of water (from 98.1° to 117.9°, 20.2% improvement) and diiodomethane (from 53.9° to 98.9°, 84.5% improvement), which contributing to the enhance of barrier properties towards O2 (30% reduction) and water as well as organic solvents. In addition, the corresponding apparent activation energy and pre-exponential factor of the direct fluorination process calculated from Arrhenius equation are 58.86kJmol−1 and 1.53×107min−1, respectively.

Space charge dynamics Of CF4 fluorinated LDPE samples from different fluorination conditions and their DC conductivities

Taking advantage of plasma technology using mixing gas CF4/H2, a fluorination process was performed on LDPE samples in the present paper. Different exposure times and discharge voltage levels were applied to produce four different types of samples. It has been found that after fluorination, space charge injection is obviously suppressed. And with longer fluorination times and higher discharge voltage, injected homocharges are reduced. By employing x-ray photoelectron spectroscopy, new chemical groups of C–F bindings are confirmed to be introduced by fluorination process of the plasma treatment. The charge suppression effect can be explained as: surface traps introduced by fluorination will reduce the interface field at both electrodes. Moreover, for fluorinated samples, heterocharge emerges obviously under 30 kV , which are considered as charges ionized from degradation products of etching and/or lower weight molecular specifies. Through the conductivity measurements also performed at 30 kV , it is found that, for the fluorinated samples with the better charge blocking effect, the conductivity is lowered. However, the conductivity of the fluorinated sample with the lightest degree of fluorination is found to be higher than that of normal samples.

Post-Mortem Investigations of Fluorinated Flame Retardants for Lithium Ion Battery Electrolytes by Gas Chromatography with Chemical Ionization

Using flame retardants (FRs) in lithium ion battery (LIB) electrolytes is usually a tradeoff between electrochemical performance and electrolyte flammability. Fluorinated FRs are a promising class of FRs which are currently under investigation. During this work, three FRs originating from triethyl phosphate with varying degree of fluorination were investigated regarding their electrochemical stability on cathode (LiNi0.33Co0.33Mn0.33O2, NCM) and anode (graphite) in half cells. During long-term cycling, changes in performance were observed. Especially on the anode side the FR addition showed a decrease in performance in comparison to the standard electrolyte (DEC/EC 1:1, 1M LiPF6). The electrolytes containing the three FRs were extracted from the cells and analyzed regarding their changes in composition and structural degradation. The decomposition products were investigated by gas chromatography (GC) with electron impact (EI) ionization and mass selective (MS) detection. To obtain more information with regard to the identification of unknown decomposition products further GC‐MS experiments with positive chemical ionization (PCI) and negative chemical ionization (NCI) were performed. Twelve different volatile organic decomposition products were identified. These decomposition products can be subdivided regarding their basic structure. Ether based, carbonate based and phosphate based fluorinated and non-fluorinated decomposition products were identified. Furthermore, possible formation pathways for all groups of decomposition products were postulated taking existing literature into account.

Fluorinated Thiophene-Based Synthons: Polymerization of 1,4-Dialkoxybenzene and Fluorinated Dithieno-2,1,3-benzothiadiazole by Direct Heteroarylation

The incorporation of fluorine atoms along the conjugated polymer backbone is an effective strategy to tune the electro-optical properties of donor–acceptor based copolymers. We report here an efficient way to synthesize and purify new mono-fluorinated thiophene derivatives for the synthesis of fluorinated dithienobenzothiadiazole (DTBT) comonomers. It was observed that the reactivity and regioselectivity of the direct (hetero)arylation polymerization (DHAP) were modified upon the amount and the positioning of the fluorine atoms on the DTBT moiety. Indeed, the polymerization time went from 66 h (for non-fluorinated DTBT, M1) to only 11 min (for tetra-fluorinated DTBT, M2). In addition to enhanced reactivity, the degree of fluorination of the flanking thiophene of the DTBT moiety also modulates the electro-optical properties, lowering both the bandgap and stabilizing the ionization energy level. Indeed, P1 (with non-fluorinated flanking thiophene) has a bandgap of 1.73 eV and an ionization energy (IE) of 4....

Effect of partial linker fluorination and linker extension on structure and properties of the Al-MOF CAU-10

The systematic investigation of the solvothermal system Al3+/5-fluoroisophthalic acid (H2mBDC-5F)/isophthalic acid (H2mBDC)/DMF/H2O through a mixed-linker approach led to new mixed-linker CAU-10 derivatives containing 11, 28 and 44% of fluorinated linker molecules (denoted as CAU-10-H/F11, CAU-10-H/F28 and CAU-10-H/F44, respectively), as determined by NMR spectroscopy. The crystal structure of CAU-10-H/F28 was determined using the Rietveld method (space group I41md, a = b = 21.3075(5), c = 10.7101(3) Å). The structure is built up by helical chains composed of cis corner-sharing AlO6 polyhedra. Each of these helices is interconnected to four adjacent helices with alternating rotational orientation through the carboxylate groups of mBDC2- linker molecules. Thus, accessible, square-shaped channels are formed. Sorption measurements revealed a high dependency of the adsorbed amount of gas on the degree of fluorination. With increasing fluorination, the total uptake decreases in N2, H2 and H2O sorption experiments and the hydrophobic character of the pores increases.In addition, an extended CAU-10 derivative, CAU-10-HTATB, was discovered using the tricarboxylic acid 4,4′,4″-s-triazine-2,4,6-triyl-tribenzoic acid (H3TATB) during the high-throughput investigation of the system Al3+/H3TATB/DMF/H2O. This new MOF, which was denoted CAU-10-HTATB, was thoroughly characterized using IR spectroscopy, thermogravimetric and elemental analysis, temperature dependent powder X-ray diffraction (PXRD) and sorption measurements. Although the compound is thermally stable up to 400 °C according to temperature-dependent PXRD measurements, it is not porous towards N2 molecules. The structure of CAU-10-HTATB could be also refined from PXRD data using the Rietveld method (space group I41/a, a = b = 36.438 (1), c = 10.9373 (9) Å).

Indolo[3,2-b]indole-Containing Donor–Acceptor Copolymers for High-Efficiency Organic Solar Cells

The organic solar cell (OSC) performance of a series of new donor–acceptor copolymers containing indolo[3,2-b]indole as a key donor block and benzothiadiazole (BT) units with various degrees of fluorination as acceptors is reported. Compared with the simple carbazole unit, the strategically developed indolo[3,2-b]indole unit is found to significantly extend π-conjugation and thus increase the intermolecular interactions of the resulting copolymer, as probed by density functional theory calculations, photophysical studies, and structural/morphological analyses. In addition, fluorination of BT can facilitate nanostructuring of the copolymers, mainly due to further planarization of the backbone, which leads to apparently higher hole/electron charge carrier mobilities. The OSC properties of this series of new copolymers blended with fullerene show a strong dependence on the fine and continuous fibrous nanostructure of the blend film. The indolo[3,2-b]indole-based copolymer with singly fluorinated BT units possesses optimal intermolecular interactions and achieves the highest power conversion efficiency of 8.84% under AM 1.5G illumination. This result shows the potential of π-extended carbazole moieties for achieving high-performance OSCs with many of the favorable properties induced by large heteroacene blocks.

Structure, magnetic properties and thermal sublimation of fluorinated Fe4 Single-Molecule Magnets

Fluorinated tetrairon(III) Single-Molecule Magnets (SMMs) [Fe4(L1)2(dpmF6)6] (1dpmF6), [Fe4(L2)2(dpmF6)6] (2dpmF6), and [Fe4(L2)2(pta)6] (2pta) were assembled combining the tripodal ligands H3L1=2-hydroxymethyl-2-phenylpropane-1,3-diol and H3L2=S-5-hydroxy-4,4-bis(hydroxymethyl)pentyl ethanethioate with fluorinated β-diketones analogues of dipivaloylmethane (Hdpm), namely 1,1,1-trifluoro-2,6,6-trimethyl-2-(trifluoromethyl)heptane-3,5-dione (HdpmF6) and pivaloyltrifluoroacetone (Hpta). The new compounds, along with [Fe4(L1)2(dpm)6] (1dpm) and [Fe4(L1)2(pta)6] (1pta), were designed in order to investigate the effect of fluorination degree on processability by thermal sublimation. The two different functional groups on the tripodal ligands, i.e. C6H5 in H3L1 and (CH2)3SAc in H3L2, are suitable for promoting physisorption and chemisorption on surfaces, respectively. Direct current magnetic data are typical for the metal-centred triangular topology of Fe4 complexes, with antiferromagnetic nearest-neighbour coupling constants in the range 16–18cm−1 and an S=5 ground spin state. Alternating current susceptibility measurements showed that slow magnetic relaxation persists in fluorinated compounds. When heated in high vacuum (10−7mbar), 2dpmF6 and 2pta undergo thermal decomposition before subliming, while 1dpmF6 was found to sublimate at 497±5K in the same conditions, being the third sublimable SMM of this family after 1pta (440±5K) and 1dpm (500±10K).